One-Step and Templateless Electropolymerization Process Using Thienothiophene Derivatives To Develop Arrays of Nanotubes and Tree-like Structures with High Water Adhesion

Abstract

Here, we report for the first time the possibility to obtain not only arrays of nanotubes but also tree-like structures with high water adhesion using a one-step and templateless electropolymerization process. Using thienothiophene derivatives, particularly thieno[2,3-b]thiophene (Thienothiophene-1) and thieno[3,2-b]thiophene (Thienothiophene-2), we demonstrate this surface fabrication in organic solvent (dichloromethane) and without any surfactants. The formation of nanotubes is due to the stabilization by the polymer of gas bubbles produced in situ during electropolymerization process, and we show that the water content plays an important role in the formation of gas bubbles even if it is not the unique parameter. Using cyclic voltammetry as an electropolymerization method, the amount of released gas is more significant, but at constant potential it is much easier to control the nanotube formation. It is also possible to obtain arrays of tree-like structures when electropolymerizing with high deposition charges, and the resulting surfaces have high θw with extremely high water adhesion even if the polymers are intrinsically hydrophilic (θ(Y)w ≈ 70°). This work is extremely important for potential applications in water transportation and harvesting, oil/water separation membranes, energy systems, and biosensing.

A Templateless Electropolymerization Approach to Nanorings Using Substituted 3,4‐Naphthalenedioxythiophene (NaPhDOT) Monomers

“…Monomer synthesis : The strategy used here to obtained substituted NaphDOT was inspired than that reported for substituted PheDOT . The monomers were obtained in five steps from 2,3‐naphthalenediol.…”

“…Very recently, we demonstrated the possibility to prepare arrays of vertically aligned nanotubes in organic solvent (dichloromethane, for example) and without any surfactant . Here, trace water present naturally in organic solvent is sufficient to produce gas bubbles . In this process, the role of the monomer is fundamental because it has also to play the role of the surfactant that means it has to stabilize the gas bubbles sufficiently long to allows the polymerization of the polymer around the bubbles.…”

Electrodeposited Poly(thieno[3,2‐b]thiophene) Films for the Templateless Formation of Porous Structures by Galvanostatic and Pulse Deposition

“…One of the greatest advantages of electropolymerization is that it permits the formation of varied surfaces morphologies, including nanosheets, nanofibers, nanospheres, cauliflower‐like structures, and even smooth surfaces with tunable wettability. Although many monomers present high stability to the electrochemistry parameters, the morphology of others may be easily changed by adjusting the electrolyte or temperature, for example …”

“…Previously, it was demonstrated that arrays of vertically aligned nanotubes with extremely high water adhesion could be obtained by using an appropriate monomer and electrochemical conditions, without a template, . More precisely, the presence of trace water in solution could lead to the formation of different gases (O 2 and/or H 2 ) following the potential ranges used during polymerization and, as a consequence, highly influence the surface morphology and hydrophobicity.…”

Nanofold‐decorated surfaces from the electrodeposition of di‐alkyl‐cyclopentadithiophenes

“…Of note among this type of surface development is the electrochemical polymerization of aromatic monomers to form conducting polymer films, which is a reliable, cost‐effective, and easily used technique. Attesting to the versatility of this technique is the wide variety of surface morphologies previously demonstrated with this approach including nanofibers, globular agglomerates, and nanotubes . Various functional monomer classes, including pyrroles, anilines, pyrenes, and thiophenes have been explored for this purpose.…”